US3679481A - Process of manufacturing sintered carrier type negative electrodes for alkaline storage cells - Google Patents
Process of manufacturing sintered carrier type negative electrodes for alkaline storage cells Download PDFInfo
- Publication number
- US3679481A US3679481A US119867A US3679481DA US3679481A US 3679481 A US3679481 A US 3679481A US 119867 A US119867 A US 119867A US 3679481D A US3679481D A US 3679481DA US 3679481 A US3679481 A US 3679481A
- Authority
- US
- United States
- Prior art keywords
- carrier
- nickel
- cadmium
- hydroxide
- oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title abstract description 34
- 230000008569 process Effects 0.000 title abstract description 18
- 210000000352 storage cell Anatomy 0.000 title description 19
- 238000004519 manufacturing process Methods 0.000 title description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical class [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 33
- 239000000243 solution Substances 0.000 abstract description 33
- PLLZRTNVEXYBNA-UHFFFAOYSA-L cadmium hydroxide Chemical compound [OH-].[OH-].[Cd+2] PLLZRTNVEXYBNA-UHFFFAOYSA-L 0.000 abstract description 30
- 238000010438 heat treatment Methods 0.000 abstract description 16
- 229910000480 nickel oxide Inorganic materials 0.000 abstract description 16
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 abstract description 16
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 abstract description 15
- 238000001035 drying Methods 0.000 abstract description 14
- 238000007654 immersion Methods 0.000 abstract description 14
- 239000007788 liquid Substances 0.000 abstract description 14
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 abstract description 14
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 10
- 239000007774 positive electrode material Substances 0.000 abstract description 8
- 239000012266 salt solution Substances 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 239000000969 carrier Substances 0.000 abstract description 6
- 239000007864 aqueous solution Substances 0.000 abstract description 5
- 239000002244 precipitate Substances 0.000 abstract description 5
- 230000001376 precipitating effect Effects 0.000 abstract description 5
- 230000003071 parasitic effect Effects 0.000 abstract description 4
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 abstract description 3
- 150000001340 alkali metals Chemical class 0.000 abstract description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical class [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 abstract description 3
- 230000002939 deleterious effect Effects 0.000 abstract description 3
- 229910052793 cadmium Inorganic materials 0.000 abstract description 2
- 239000012050 conventional carrier Substances 0.000 abstract description 2
- 239000007772 electrode material Substances 0.000 abstract description 2
- -1 CADMIUM HYDROXIDES Chemical class 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 42
- 239000011148 porous material Substances 0.000 description 22
- 229910052759 nickel Inorganic materials 0.000 description 16
- 230000006872 improvement Effects 0.000 description 15
- 238000001556 precipitation Methods 0.000 description 13
- 238000005406 washing Methods 0.000 description 10
- 239000011149 active material Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 9
- 239000012670 alkaline solution Substances 0.000 description 7
- 238000005470 impregnation Methods 0.000 description 7
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 7
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 210000004027 cell Anatomy 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 150000001661 cadmium Chemical class 0.000 description 4
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 150000004679 hydroxides Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 229910000011 cadmium carbonate Inorganic materials 0.000 description 1
- 229940065285 cadmium compound Drugs 0.000 description 1
- 150000001662 cadmium compounds Chemical class 0.000 description 1
- GKDXQAKPHKQZSC-UHFFFAOYSA-L cadmium(2+);carbonate Chemical compound [Cd+2].[O-]C([O-])=O GKDXQAKPHKQZSC-UHFFFAOYSA-L 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005262 decarbonization Methods 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/24—Electrodes for alkaline accumulators
- H01M4/26—Processes of manufacture
- H01M4/28—Precipitating active material on the carrier
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the resultant negative electrode has a materially reduced amount of deleterious or parasitic positive active material and increased porosity and flexibility as compared with like negative electrodes produced by conventional carrier impregnating and precipating procedure.
- Negative electordes resulting from the process of this invention and alkaline storage cells with such negative electrodes are also disclosed.
- This invention relates to improvements in the manufacture of negative electrodes comprising sintered porous metallic carriers bearing active negative material intended for use in alkaline storage cells and more especially to the manufacture of negative electrodes whose active negative material is a cadmium compound such as cadmium hydroxide and which are particularly useful in sealed cells.
- the invention also relates to the electrodes resulting from the method of this invention and to electrochemical storage cells containing such electrodes.
- the conventional manufacturing method for negative electrodes whose active material is cadmium hydroxide consists in impregnating a sintered porous nickel carrier with a solution of a cadmium salt, preferably cadmium nitrate which is slightly acidified, e.g. by nitric acid, into which the carrier is immersed or dipped, then in immersing the thus impregnated carrier in an alkaline solution e.g. of potassium hydroxide or preferably sodium hydroxide, preferably at high temperature in order to precipitate cadmium hydroxide in the pores of the carrier. This procedure is usually repeated several times until a suitably selected amount of cadmium hydroxide has been deposited in the pores of the sintered carrier.
- a cadmium salt preferably cadmium nitrate which is slightly acidified, e.g. by nitric acid
- This phenomenon may occur at the end of the discharge in the cell having the smallest capacity among the cell of a battery.
- Objects and features of the present invention are to remedy these drawbacks and make possible the manufacture of sintered carrier type negative electrodes that are substantially free of undesired positive active materials without at the same time introducing any other impurities.
- the heating step is effected at a temperature of about 250 C. for a period of about one hour.
- the nickel oxide and cadmium oxide bearing electrode carriers are submitted to a rehydrating step and finally washed and dried.
- the rehydrating step comprises immersion of the nickel oxide and cadmium oxide bearing porous carriers in a heated aqueous liquid such as pure (distilled) water maintained at a temperature of about 80 C. or more preferably a dilute aqueous solution of nickel sulfate at a concentration advantageously of about 2.5 g./l. alsomaintained at said temperature of about 80 C. or alternatively in a sodium hydroxide solution at a concentration advantageously of about 250 g./l. also maintained at said temperature of about 80 C.
- the immersion in the selected heated aqueous liquid may be maintained for from approximately 1 to approximately 2 hours.
- practice of the processaccording to the invention has an additional advantage in that it facilitates the elimination of residual nitrates remaining in the product resulting from the two conventional preliminary conventional impregnation and precipitation steps by simple washing because such nitrates are thus made soluble, so that the usually required electrochemical purification procedure of electrodes produced by the conventional impregnation and precipitation steps only and consisting in cathodically and anodically polarizingsuch electrodes in an alkaline solution in order to rid them of their impurities, which usually follow the impregnation and precipitation steps of the conventional method becomes unnecessary.
- the negative electrodes produced in accord with the practice of the method of the invention present an increased flexibility over the electrode product of the said conventional method. This is very advantageous especially when such electrodes are to be used for manufacturing cells with wound electrodes.
- the flexibility of electrodes resulting from conventional impregnation and precipitation procedure (which may be tested by the deflection of a resulting electrode held at one end and submitted at the other end to an increasing load) is doubled by the subsequent electrochemical purifying procedure hereinabove mentioned as compared with an electrodewhich has not been so purified, I have found that this flexibility is increased three times in electrodes prepared according to the method of this invention employing the said heating step at 250 C. followed by a rehydration step in a sodium hydroxide solution.
- Negative electrodes prepared according to this invention are therefore advantageous because of their superior 4 porosity, flexibility and relative freedom of presence of active positive materials in substantial and deleterious amounts as well as freedom from other impurities.
- a band or strip of porous sintered nickel carrier material in conventional manner is immersed in an acidified salt solution of the desired active material, for example, a solution of cadmium nitrate to impregnate its pores, followed by immersion in an alkaline solution, for 'example, of sodium hydroxide at elevated temperature to precipitate cadimum hydroxide in the pores of the carrier, this precipitation being accompanied, too, by precipitation into the carrier pores of the nickel from the carrier which has been attacked by the impregnation solution and its conversion into nickel hydroxide by said alkaline soluton, said two immersion steps being repeated as needed for several times in seriatim until a desired quantity of cadmium hydroxide deposit has been effected in the pores of the carrier accompanied, of course, by precipitation of parasitic and'undesirable nickel hydroxide from the nickel of the carrier.
- an acidified salt solution of the desired active material for example, a solution of cadmium nitrate to impregnate its pores
- the precipitate bearing carrier product of these impregnation and precipitation steps is then washed and dried and further subjected to a heating step in air at about 250 C. for about one hour to etfect conversion of the precipitated nickel hydroxide and cadmium hydroxide into nickel oxide and cadmium oxide.
- a rehydration step is effected by immersion of the nickel oxide and cadmium oxide bearing carrier product of said heating step in an aqueous nickel sulfate solution having a concentration of about 2.5 g./l. maintained at a temperature of about C.
- Example II The procedure of Example I is followed with a similar 7 pregnating and precipitating procedure and with a further,
- Alkaline storage cells utilizing negative electrodes resulting from the practice of this invention may be assembled together with suitable positive electrodes and interposed separators and with conventional alkaline electrolytes.
- the electrode-separator assemblies may be spirally wound, if desired, and in all event enclosed in appropriate sealed containers in known manner.
- Negative electrodes resulting from the practice of this invention are highly porous and flexible and comprise a sintered porous nickel carrier whose pores include as active negative material finely divided cadmium hydroxide and also include some inert nickel oxide as impurity but are substantially free of other impurities.
- That improvement in the process of manufacturing a negative electrode for alkaline storage cells comprising the steps of providing a porous nickel carrier, impregnating pores of the carrier with a cadmium salt solution, then precipitating cadmium hydroxide in said pores accompanied by precipitation of some nickel hydroxide from attached nickel of the carrier by immersion of the impregnated carrier in an alkaline solution, subsequently washing and drying the multi-hydroxide bearing carrier, heating the multi-hydroxide bearing carrier after said drying to a temperature ranging from 200 C. to 500 C.
- aqueous liquid is nickel sulfate solution having a concentration of approximately 2.5 g./l. 6. That improvement in the process of manufacturing a negative electrode for alkaline storage cells according to claim 1 wherein said aqueous liquid is a sodium hydroxide solution having a concentration of approximately 250 g./l.
- said porous metallic carrier is a band or strip of 'sintered nickel, wherein said metallic salt solution is an acidified cadmium nitrate solution, wherein said alkaline solution is an alkali metal hydroxide solution, wherein said first-named metallic hydroxide is cadmium hydroxide and said second-named hydroxide is nickel hydroxide and wherein said aqueous liquid for said rehydration is selected from the group consisting of water, nickel sulfate solution and sodium hydroxide solution.
- the duration of said rehydration is from approximately 1 to approximately 2 hours.
- aqueous liquid is a sodium hydroxide solution having a concentration of approximately 250 g./l.
- That improvement in the process of manufacturing 8 a a negative electrode for an alkaline storage cell comprising the steps of providing a porous sintered nickel carrier strip, immersing said strip in an acidified cadmium nitrate solution to impregnate pores of said carrier strip, then immersing the so-impregnated carrier strip into an alka-.
- aqueous solution is sodium hydroxide at a concentration of 250 g./l. and the last-named drying is etfected in decarbonated air.
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR7010933A FR2082771A5 (fr) | 1970-03-26 | 1970-03-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3679481A true US3679481A (en) | 1972-07-25 |
Family
ID=9052948
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US119867A Expired - Lifetime US3679481A (en) | 1970-03-26 | 1971-03-01 | Process of manufacturing sintered carrier type negative electrodes for alkaline storage cells |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US3679481A (fr) |
| AU (1) | AU2699071A (fr) |
| BE (1) | BE764139A (fr) |
| CA (1) | CA981332A (fr) |
| DE (1) | DE2106130A1 (fr) |
| FR (1) | FR2082771A5 (fr) |
| GB (1) | GB1279587A (fr) |
| LU (1) | LU62751A1 (fr) |
| NL (1) | NL7104066A (fr) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4032697A (en) * | 1974-05-20 | 1977-06-28 | Bell Telephone Laboratories, Incorporated | Methods of producing electrodes for alkaline batteries |
| US4139423A (en) * | 1978-04-07 | 1979-02-13 | General Electric Company | Sintered negative plate |
| US4166010A (en) * | 1978-04-07 | 1979-08-28 | General Electric Company | Sintered negative plate |
| US5401460A (en) * | 1993-11-23 | 1995-03-28 | M-C Power Corporation | Method for sintering fuel cell electrodes using a carrier |
| US5833452A (en) * | 1994-12-15 | 1998-11-10 | M-C Power Corporation | Coated metal sintering carriers for fuel cell electrodes |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2343595C1 (ru) * | 2007-10-22 | 2009-01-10 | Иршат Атауллович Махмутов | Способ изготовления безламельного кадмиевого электрода |
-
1970
- 1970-03-26 FR FR7010933A patent/FR2082771A5/fr not_active Expired
-
1971
- 1971-02-10 DE DE19712106130 patent/DE2106130A1/de active Pending
- 1971-03-01 US US119867A patent/US3679481A/en not_active Expired - Lifetime
- 1971-03-09 LU LU62751D patent/LU62751A1/xx unknown
- 1971-03-11 BE BE764139A patent/BE764139A/fr unknown
- 1971-03-16 CA CA107,936A patent/CA981332A/en not_active Expired
- 1971-03-25 NL NL7104066A patent/NL7104066A/xx unknown
- 1971-03-25 AU AU26990/71A patent/AU2699071A/en not_active Expired
- 1971-04-19 GB GB24601/71A patent/GB1279587A/en not_active Expired
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4032697A (en) * | 1974-05-20 | 1977-06-28 | Bell Telephone Laboratories, Incorporated | Methods of producing electrodes for alkaline batteries |
| US4139423A (en) * | 1978-04-07 | 1979-02-13 | General Electric Company | Sintered negative plate |
| US4166010A (en) * | 1978-04-07 | 1979-08-28 | General Electric Company | Sintered negative plate |
| US5401460A (en) * | 1993-11-23 | 1995-03-28 | M-C Power Corporation | Method for sintering fuel cell electrodes using a carrier |
| US5833452A (en) * | 1994-12-15 | 1998-11-10 | M-C Power Corporation | Coated metal sintering carriers for fuel cell electrodes |
Also Published As
| Publication number | Publication date |
|---|---|
| GB1279587A (en) | 1972-06-28 |
| LU62751A1 (fr) | 1971-08-23 |
| NL7104066A (fr) | 1971-09-28 |
| CA981332A (en) | 1976-01-06 |
| FR2082771A5 (fr) | 1971-12-10 |
| DE2106130A1 (de) | 1971-10-14 |
| BE764139A (fr) | 1971-09-13 |
| AU2699071A (en) | 1972-09-28 |
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